Emulsifier compositions



United States Patent 3,506,588 EMULSIFIER COMPOSITIONS Edgar Selz,Evanston, Ill., assignor to Witco Chemical Corporation, Inc., New York,N.Y., a corporation of Delaware No Drawing. Continuation-impart ofapplication Ser. No. 324,251, Nov. 18, 1963. This application Apr. 24,1968, Ser. No. 723,870

Int. Cl. A0lm 21/00; A01n 17/00; B01f 17/00 US. Cl. 252355 8 ClaimsABSTRACT OF THE DISCLOSURE Emulsifier compositions, having particularutility for use in toxicant concentrates, said emulsifier compositionscomprising essentially clear liquids at room temperature and containingan acetonitrile-soluble and water-soluble to readily water-dispersiblenonionic emulsifier of the type which includes in its molecule ahydrophobic group and at least 8 oxyethylene groups, said compositionscontaining acetonitrile in proportions of from 1 to 20%, by weight, ofthe emulsifier composition.

Water-soluble or readily water-dispersible nonionic emulsifiers of thetype which contain a number of recurring oxyethylene groups or unitshave long been known and are in widespread use. They take many formsbut, in at least most cases, they are characterized by containing, intheir molecules, a total of from 8 to or and not uncommonly up to about60 or more oxyethylene groups which are linked, in the molecule of thesaid nonionic emulsifier, directly or indirectly, that is, through otherlinkages, to a higher molecular weight hydrophobic radical containingfrom 8 to 26 carbon atoms, said hydrophobic radical commonly being inthe form of an alkyl radical or a monocarboxylic acid acyl radicalcontaining from 8 to 26 carbon atoms, particularly from 12 to 16 carbonatoms; or an alkylated aryl radical, notably an alkylated benzene,toluene, phenol, or naphthalene radical containing from 12 to 26 carbonatoms, particularly from 15 to 22 carbon atoms. Especially desirablenonionic emulsifiers for use in the practice of my present invention are15 to 30 mol ethylene oxide adducts of nonyl phenol or mixtures ofethylene oxide adducts of nonyl phenol with different contents ofethylene oxide, advantageously within the aforesaid areas.

It is also well known in the art to utilize the aforesaid nonionicemulsifiers in conjunction with anionic emulsifiers and to market themas emulsifiers compositions dissolved or dispersed in organic solventsor mixtures of organic solvents. Typical of such anionic emulsifiers, ofwhich large classes and large numbers of such classes are well known tothe art, are higher molecular weight, generally C C alkyl sulfates suchas dodecyl sulfate in the form of such salts as the sodium salt and themonoethanolamine, diethanolamine, triethanolamine and isopropanolaminesalts; the higher molecular weight, generally C C alkyl benzene andalkyl naphthalene sulfonates such as dodecyl benzene sulfonate, tridecylbenzene sulfonate, pentadecyl benzene sulfonates and the correspondingalkyl naphthalene sulfonates, in the form of the aforementioned salts asWell as the calcium and magnesium salts; sulfopolycarboxylic acid estersof higher colecular weight, generally CrC fatty acid amides of alcoholprimary or secondary amines such as sulfosuccinic acid esters of lauricand myristic acid amides of monoethanolamine, diethanolamine andmonoisopropanolamine, in the form of their alkali metal, ammonium, andamine salts such as the isopropylamine salt, and the half alkalimetal-half amine salts such as the half ammonium-half isopropylaminesalt of the sulfosuccinic acid ester of the oleic acid amide ofmonoisopropanolamine; the sulfates of higher molecular weight (generallyC to C fatty acid monoglycerides exemplified by the monosulfates oflauric or myristic or coconut oil mixed fatty acid monoesters ofglycerine, in the form of their alkali metal, ammonium or amine salts;and phosphoric acid esters of 25 to 35 mol ethylene oxide adducts ofnonyl phenol. Especially desirable anionic emulsifiers for use in thepractice of my present invention are calcium and lower amine salts ofmonododecyl benzene monosulfonic acid, examples of the latter beingisopropylamine salts and aminoethylethanolamine salts of monododecylbenzene monosulfonic acid.

The aforesaid types of emulsifiers and emulsifier compositions are, asindicated above, commonly marketed as such as well as in the form oftoxicant-containing concentrates, said concentrates being intended foradmixture with water to produce aqueous emulsions or dispersions whichare applied to plants, earth soils and like agricultural environments aspesticides or insecticides, soil fumigants, nematocides, herbicides,fungicides, rodenticides, miticides, disinfectants and the like,hereafter, for convenience, designated simply as toxicants.

Emulsifiers and emulsifier compositions of the foregoing typesespecially, and to a somewhat lesser extent toxicant concentratescontaining the same, although in widespread commercial use, neverthelesshave numbers of objections. Many such emulsifier compositions, forinstance, although producing excellent dispersions in aqueous media forapplication to plants, insects, etc., when used in producing toxicantconcentrate formulations, tend, on storage or in shipment and even whenfreshly prepared, to separate into layers or to thicken. This isparticularly the case where said compositions stand over a period oftime in storage or during shipment and is aggravated by low temperatureconditions. -While this does not destroy their ultimate usefulness, itfrequently renders difiicult their handling and it also has definiteobjections from the standpoint of the appearance of the compositions. Inan effort to solve these problems, it has been common practice to addvarying amounts, for instance from 3 to 20% by weight of the emulsifiercompositions, of methanol or denatured ethanol to maintain thecompositions in a fluid state. For a variety of reasons, this practiceis not entirely satisfactory. Attempts to replace the methanol ordenatured ethanol have resulted in additional objections such asexcessive quantities of the attempted replacements, for instance,n-propanol and isopropanol, being required, and lack of clarity of theemulsifier compositions and toxicant concentrates.

I have discovered that acetonitrile is unusually and unexpectedlyeffective as a solvent in emulsifier compositions of the type which Ihave described above, especially where the non-ionic emulsifier of thetype referred to above and discussed in further detail below is a solidat room temperatures or below. In the first place, it maintains theemulsifier composition in a fluid or mobile state over prolonged periodsof time. In addition, it imparts much greater clarity to the emulsifiercompositions than even the methanol and the denatured ethanol. Finally,in

various emulsifier compositions, its use eliminates or sharply reduceslayer separations. It is especially efficaci- Ous in emulsifiercompositions and toxicant concentrates containing the same where thenonionic emulsifier employed is or includes one or more which is a solidat or below room temperatures. The acetonitrile may be used as the soleorganic liquid in which the nonionic emulsifier, or nonionic emulsifierand anionic emulsifier, are dissolved. In such case, high emulsifierconcentrations can be made which still retain good mobility or liquidityeven at relatively low temperatures. It is, however, especiallydesirable that the acetonitrile be employed in conjunction with one ormore organic solvents, particularly hydrocarbons, of the type which arecommonly utilized in emulsifier compositions. These include, amongothers, benzene, toluene, xylene, aromatic naphthas, methylatednaphthalenes, tetrahydronaphthalene, cyclohexane, kerosene, dipropyleneglycol methyl ethers, and n-propanol. These and various other organicsolvents are frequently sold under trade names such as Cyclosol 53,which is a xylene type solvent, Sovacide 544C, which is an aromaticpetroleum oil containing methylated naphthalenes; Varsol, which is astraight petroleum solvent; Certrex 47 (which is a highly aromatic oil);and Solvesso 150, which is derived from petroleum and has a high contentof aromatic hydrocarbons. Still other organic solvents which can be usedin the emulsifier compositions of the present invention are disclosed invarious of the patents referred to below.

The acetonitrile is generally utilized in proportions of the order of 1to 20%, by weight, and particularly desirably from 2 to 8%, of theemulsifier composition as a whole. When the content of normally solidnonionic emulsifier is at least 50%, by weight, of the emulsifiercontent of the emulsifier composition, it is particularly desirable thatthe acetonitrile be present in proportions of at least and, betterstill, from 5 to 10%, by weight, of the emulsifier composition as awhole. In terms of proportions based on the total organic solventcontent used in the emulsifier compositions, the acetonitrile maycomprise at least 10% and, better still, of the order of to 50%, byweight, of the total organic solvent content and, indeed, as statedabove, even all of the organic solvent content. In toxicant concentratesmade by utilization of the emulsifier compositions of the presentinvention, the acetonitrile will be present in proportions in the rangeof 0.04 to 2% and, better still, in the range of 0.1 to 0.8%, by weight,of the toxicant concentrate composition as a whole.

Nonionic emulsifiers useful in emulsifier compositions, and toxicantconcentrates containing the same, to which my present invention relatesare disclosed, by way of example, in US. Patents Nos. 2,447,475;2,509,233; 2,552,- 187; 2,588,318; 2,731,338; 2,872,368; 2,875,128;2,993,- 830; 3,046,153; 3,071,550; 3,074,791; 3,095,353; 3,097,- 173;3,098,789; and Reissue No. 24,184.

While, in the nonionic emulsifiers which are utilized in the emulsifiercompositions of my present invention, the hydrophobic portion of themolecule is generally an alkyl or monocarboxylic, particularly fatty,acid acylradical, this need not be the case. The hydrophobic portion ofthe molecule may be imparted by recurring oxypropylene, oxybutylene andhigher oxyalkylene groups. Thus, for instance, the hydrophobic functionmay be achieved by six or more recurring oxypropylene groups where n isat least 6 so that the polyoxypropylene radical will contain at least 18carbon atoms. Where the polyoxyalkylene radical is oxyhexylene, thenumber of such recurring groups may be as low as 3 and, again,therefore, the oxyalkylene radical will contain at least 18 carbonatoms. Typical nonionic emulsifiers of this latter type are thosedisclosed, by way of illustration, in Patents Nos.

' 2,674,619 and 2,875,128, the nonionic emulsifiers of saidlast-mentioned patent being in the form of oxyethylatedoxypropylatedglycerin wherein polyoxypropylene chains are attached to the glycerinenucleus and polyoxyethylene chains are in turn attached to saidpolyoxypropylene chains, the terminal group being hydroxyl groups of thepolyoxyethylene chains, the oxypropylene groups forming 48% to 66% ofthe total oxyalkylene groups, the oxyalkylated glycerine containingabout 83-126 mols of propylene oxide per mol of glycerine and furthercontaining about 48135 mols of ethylene oxide per mol of glycerine. Inplace of glycerine, other aliphatic polyhydric alcohols can be used forthe polyoxypropylation-polyoxyethylation reaction to produce thenonionic emulsifiers of this particular type, among such polyhydricalcohols being ethylene glycol, diethylene glycol, polyglycerols such asdiglycerol, triglycerol, tetraglycerols, and mixtures thereof, sorbitol,mannitol, arabitol, sorbitan, mannitan, pentaerythritol,dipentaerythritol, and the like.

While polyoxypropylene, polyoxybutylene and higher polyoxyalkylenegroups can be present in the molecule of the nonionic emulsifier, theremust be in all cases sufficient polyoxyethylene groups in the moleculeof the nonionic emulsifier to render the same either Water-soluble orreadily water-dispersible irrespective of whether the hydrophobicportion of the molecule is represented by alkyl radicals ormonocarboxylic acid acyl radicals containing from 8 to 26 carbon atoms,or alkylated aryl radicals containing from 12 to 26 carbon atoms, orpolyoxyalkylene radicals in which the recurring oxyalkylene groupsthereof contain from 3 to 6 carbon atoms and in which any saidpolyoxalkylene radicals contain at least 3 of such recurring oxalkylenegroups, generally derived from 1,2-propylene oxide or higher alkyleneoxides or a-epoxides such as butylene oxide, pentylene oxide andhexylene oxides, or combination of such radicals.

The nonionic emulsifiers Whose use is contemplated by my presentinvention are those which are water-soluble to readily water-dispersibleand which are soluble in acetonitrile, or in the combination of organicsolvents containing acetonitrile where the acetonitrile is used inadmixture which other organic solvents, particularly hydrocarbonsolvents, at the temperature involved, namely, the temperatures at whichthe compositions are used or to which they are subjected in storage,transportation or shipping or the like.

Among such nonionic emulsifiers are alkyl phenoxy polyoxyethyleneethanols, ethylene oxide condensates, polyoxyethylated fatty alcohols,polyethylene glycol esters of fatty acids, alkyl aryl polyoxyethyleneethers, polyoxyethylene alkyl alcohols, polyoxyethylated vegetable oils,polyoxyethylene sorbitant esters of fatty acids, alkyl ethers andthioethers of polyoxyethylene glycols, monocarboxylic and particularlyfatty acid esters of polyoxyethylene glycols, Where the alkyl, fattyalcohol and fatty acid radicals contain from 8 to 26 carbon atoms, andthere are present in the molecule of the noionic emulsifier sufficientoxyethylene groups, at least 8 in number, to render said nonionicemulsifier water-soluble to readily water-dispersible.

While the emulsifier compositions contemplated by the present inventionin its broadest aspect may comprise one or more nonionic emulsifiers ofthe type described above dissolved in acetonitrile, its major advantagesreside in emulsifier compositions containing, in addition to one or moreof the aforesaid types of nonionic emulsifiers, one or more anionicemulsifiers, preferably one or more watersoluble or somewhatwater-dispersible anionic emulsifiers and one or more organic solventsin addition to the acetonitrile. The anionic emulsifier selected shouldbe soluble in the mixture of ingredients making up the emulsifiercomposition as a whole, as well as in the toxicant concentratecompositions in which said emulsifier compositions are incorporated.

Anionic emulsifiers of the type which are utilized in the emulsifiercompositions of my present invention are well known in the art andillustrative examples thereof have been referred to above. They aredisclosed in large numbers of patents and other publications. Various ofthe patents mentioned above in connection with disclosures of knownnonionic emulsifiers also disclose typical anionic emulsilers which canbe used in the emulsifier compositions, and toxicant concentratescontaining the same, with which my present invention is concerned, andadditional anionic emulsifiers are disclosed in numerous other patentsof which the following may be mentioned: 2,976,209; 2,976,211 and3,080,280.

Where anionic emulsifiers are used together with the aforesaid types ofnonionic emulsifiers, generally speaking, in most cases the nonionicemulsifier or emulsifiers will be used in amounts in excess of theamounts of the anionic emulsifier or emulsifiers. However, this mayvary, and the amount of the anionic emulsifier or emulsifiers may begreater than the amount of the nonionic emulsifier or emulsifiers incertain systems for optimum results. In general, the ratio, by weight,of the nonionic emulsifier or emulsifiers to the anionic emulsifier oremulsifiers may range from 95:5 to 5:95 with a particularly useful rangeof ratios, in most cases, from 75 :25 to 25 :75.

As I have indicated above, the emulsifier compositions of the presentinvention have especially significant utility for use in toxicantconcentrates. Numerous toxicants can be utilized to produce toxicantconcentrates which, per se, are well known to the art, and inconjunction with which the emulsifier compositions of my presentinvention are effectively employed. Such toxicants include, amongothers, chlordane, aldrin, dieldrin, lindane, heptachlor, nemagon, DDT,toxaphene, methoxychlor, alkyl aryl sulfite (Aramite) organicthiocyanates such as [i-butoxy B'-thiocyanoethyl ether, lower alkylethers of pentachlorophenol, parathion, malathion,p-nitropenylthiophosphoric acid diethyl ester, DDVP(dimethyldichloro-vinyl phosphate), phosdrin (dimethylcarbomethoxymethylvinyl phosphate) and bidrin (dimethyl phosphate of 3-hydroxy-N,N-dimethyl-cis-crotonamide). Generally speaking, the toxicants withwhich the emulsifier compositions of my invention can be utilized are ofthe type which are organic solvent-soluble and substantially insolubleor difficulty dispersible in water. However, toxicants such as DDVP,phosdrin and bidrin are soluble in water but they must be formulated assolutions in organic solvents, generally water-insoluble organicsolvents, since, in aqueous solutions, they readily hydrolyze. Thetoxicants in conjunction with which the emulsifiers of my invention areelfectively utilized can be characterized as being organicsolvent-soluble and substantially insoluble or difliculty dispersi'blein water, as well as toxicants, exemplified by DDVP, phosdrin andbidrin, which, although technically soluble in water, requireformulation in the form of organic solvent solutions to avoid hydrolysisor other breakdown of the toxicant. The foregoing, and others, aredisclosed in the various patents referred to above.

The following examples are illustrative of emulsifier compositionsfalling within the scope of my invention. Other specific embodimentswill readily occur to those skilled in the art in the light of theguiding principles and teachings disclosed herein. All parts listed areby weight:

EXAMPLE 1 Xylene 12.5 N-propanol 5 Acetonitrile 5.5

6 EXAMPLE 2 Aminoethylethanolamine salt of monododecyl benzenemonosulfonic acid (76% solution in n-pro- Half ammonium halfisopropylamine salt of the sulfosuccinic acid ester of the oleic acidamide of monoisopropanolamine 28 Antarox A-400 45 Xylene 22 Acetonitrile5 EXAMPLE 5 Sodium salt of polyoxyethylene ether monosulfonate oftertiary octyl phenol (about 17 mols of ethylene oxide) 55 16-molethylene oxide adduct of nonyl phenol 3O Certrex 47 5 Acetonitrile 10EXAMPLE 6 Calcium salt of monododecyl benzene monosulfonic acid 32 Talloil fatty acid diester of adduct of 20 mols of ethylene oxide with onemol of glycerine 48 Kerosene 1O Acetonitrile 10 EXAMPLE 7 Parts Calciumsalt of monododecyl benzene monsulfonic acid 37.5 15-mol ethyltne oxideadduct of nonyl phenol 32 2'0-mole ethylene oxide adduct of nonyl phenol16 Xylene 11.5 Acetonitrile 3 EXAMPLE 8 Aminoethylethanolamine salt ofmonododecyl benzene monosulfonic acid 39.4 15-mol ethylene oxide adductof nonyl phenol 11.3 20-mol ethylene oxide adduct of nonyl phenol c 29.1Xylene 15.2 Acetonitrile 5 EXAMPLE 9 Aminoethylethanolamine salt ofmonododecyl benzene monosulfonic acid 46.5 Butoxyethoxypolypropoxy-polyethoxy ethanol 14 12-mol ethylene oxide adduct of nonylphenol 5 15-mol ethylene oxide adduct of nonyl phenol 11.5 Xylene 20Acetonitrile 3 EXAMPLE 10 15-mol ethylene oxide adduct of nonyl phenol5O 20-mol ethylene oxide adduct of nonyl phenol 35 Acetonitrile 15EXAMPLE 11 50-mol ethylene oxide adduct of castor oil 80 Acetonitrile 20The following examples are illustrative of toxicant concentrates whichcontains typical emulsifier compositions of my present invention.

EXAMPLE 12 Toxaphene 60 Calcium salt of monododecyl benzene sulfonicacid 2.5 Refined tall oil fatty acid-18-mol ethylene oxide adduct .5Kerosene 39 Acetonitrile 1 EXAMPLE 13 DDT 25 Aminoethylethanolamine saltof monododecyl benzene sulfonic acid 1.5 20-mo1 ethylene oxide adduct ofnonyl phenol 1 15-mo1 ethylene oxide adduct of nonyl phenol 2.5 Xylene69.2 Acetonitrile 0.8

' EXAMPLE 14 Chlordane 63 Aminoethylethanolamine salt of sulfosuccinicacid ester of oleic acid amide of monoethanolamine 2 18-mol ethyleneoxide adduct of nonyl phenol 5 Varsol 28.5 Acetonitrile 1.5

EXAMPLE 15 Dieldiin 20 Nonionic emsulified prepared by reacting 1 mol ofglycerine with 60 mols of 1,2-propylene oxide followed by reacting with6 mols of ethylen oxide 3 Xylene 75 Acetonitrile 2 What is claimed asnew and desired to be protected by Letters Patent of the United Statesis:

1. An emulsifier composition, which is essentially a clear liquid atroom temperature, said composition consisting essentially of (a) anacetonitrile-soluble and watersoluble to readily water-dispersiblenonionic emulsifier containing in the molecule thereof (i) a hydrophobicgroup selected from the group consisting of alkyl and monocarboxylicacid acyl containing from 8 to 26 carbon atoms, alkylated arylcontaining from 12 to 26 carbon atoms, and polyoxyalkylene in which therecurring oxyalkylene groups thereof contain from 3 to 6 carbon atomsand in which said polyoxyalkylene contains at least 18 carbon atoms, and(ii) suflicient oxyethylene groups, at least 8 in number, to render saidnonionic emulsifier water-soluble to readily water-dispersible, and (b)acetonitrile, said acetonitrile being present in proportions from 1 to20%, by weight, of said emulsifier composition.

2. An emulsifier composition in accordance with claim 1, saidcomposition also including an anionic emulsifier and an organic solventselected from the group consisting of hydrocarbons, dipropylene glycolmethyl ethers and lower alkanols, the ratio of the nonionic emulsifierto anionic emulsifier being from 95:5 to :95.

3. An emulsifier composition according to claim 1,

wherein said nonionic emulsifier contains in .the molecule thereof atleast 8 oxyethylene groups and a higher molecular weight hydrophobicradical containing 8 to 26 carbon atoms, said composition also includingan anionic emulsifier, the ratio of the nonionic emulsifier to anionicemulsifier being from :5 to 5:95.

4. An emulsifier composition according to claim 3, wherein there is alsopresent a hydrocarbon solvent.

5. An emulsifier composition according to claim 4, wherein said nonionicemulsifier is a solid at room temperature, and wherein said acetonitrileis present in proportions from 2 to 8%, by weight, of said emulsifiercomposition.

6. An emulsifier composition according to claim 1, wherein said nonionicemulsifier contains in the molecule thereof from 15 to 30 oxyethylenegroups and a higher molecular weight hydrophobic radical containing from12 to 18 carbon atoms, said nonionic emulsifier being a solid at roomtemperature, said composition also including a C to C alkyl benzenesulfonate and an organic solvent selected from the group consisting ofhydrocarbons, dipropylene glycol methyl ethers and lower alkanols, saidacetonitrile being present in proportions from 2 to 8%, by weight, ofsaid emulsifier composition.

7. An emulsifier composition according to claim 1, wherein said nonionicemulsifier is a 15 to 20 mol ethylene oxide adduct of nonyl phenol, saidcomposition also containing a C to C alkylbenzene sulfonate, andhydrocarbon solvent, said acetonitrile being present in proportions from2 to 8%, by weight, of said emulsifier composition.

8. An emulsifier composition according to claim 1, wherein said nonionicemulsifier is an oxyethylated-oxypropylated glycerine in whichpolyoxypropylene chains are attached to the glycen'ne nucleus andpolyoxyethylene chains are in turn attached to said polyoxypropylenechains, the terminal groups being hydroxyl groups of the polyoxyethylenechains, the oxypropylene groups forming 48% to 66% of the totaloxyalkylene groups, the oxyalkylated glycerine containing about 83-126mols of propylene oxide per mol of glycerine and further containingabout 48-135 mols of ethylene oxide per mol of glycerine. I

References Cited UNITED STATES PATENTS 3,145,139 8/1964 Fearing 424-173FOREIGN PATENTS 562,527 9/1958 Canada.

OTHER REFERENCES Arthur and Elizabeth Rose, The Condensed ChemicalDictionary, p. 9, 1961.

HERBERT B. GUYNN, Primary Examiner D. L. ALBRECHT, Assistant ExaminerUS. Cl. X.R.

